CN103817466B - A kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering - Google Patents
A kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 108
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 239000010949 copper Substances 0.000 title claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- 238000005476 soldering Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 90
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000000843 powder Substances 0.000 claims abstract description 64
- 229910052786 argon Inorganic materials 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 239000000428 dust Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 43
- 238000005086 pumping Methods 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910020836 Sn-Ag Inorganic materials 0.000 claims description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 claims description 2
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 28
- 229910000679 solder Inorganic materials 0.000 description 11
- 230000007547 defect Effects 0.000 description 8
- 238000012546 transfer Methods 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering, the present invention relates to and prepares the method that Graphene strengthens copper base composite soldering.The present invention will solve conventional method and prepare when Graphene strengthens copper base composite soldering that the graphene dispersion that exists is poor, blemish is many, preparation temperature is high and inefficient problem.Method: copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, pass into hydrogen, and be at high temperature incubated, pass into argon gas again and carbon-source gas deposits, after deposition terminates, stop passing into carbon-source gas, finally be cooled to below room temperature, obtain Graphene/copper composite powder, then metal dust or alloy powder are mixed with Graphene/copper composite powder, namely obtain Graphene and strengthen copper base composite soldering.The present invention is used for a kind of efficient cryogenic and prepares the method that Graphene strengthens copper base composite soldering.
Description
Technical field
The present invention relates to and prepare the method that Graphene strengthens copper base composite soldering.
Background technology
Soldering is the one of three large welding methods (melting welding, pressure welding, soldering), mainly adopt and make solder than the low-melting metal material of mother metal, by weldment and solder heat to higher than solder fusing point, lower than mother metal fusion temperature, utilize liquid solder to soak mother metal, fill play movement and realize with the counterdiffusion of mother metal phase the method being connected weldment.In numerous areas all extensive application such as machinery, motor, instrument, electronic technology.The performance indications such as intensity, hardness, heat resistance, corrosion resistance of soldered fitting all have direct relation with solder, add the reinforcements such as particle, fiber, synusia and can effectively improve soldered fitting performance in solder.Along with the development of science and technology, nano material (as nano particle, nano wire, nanometer sheet etc.) strengthens as reinforcement the study hotspot that solder has become welding field.
Graphene is a kind of new material of the individual layer laminated structure be made up of carbon atom.Due to the particularity of graphene-structured, compared with other materials, Graphene has outstanding electric property, thermal property and mechanical performance.Huge application prospect is shown in all many-sides such as electronic device, composite and electrochemical energy storage materials.There are some researches prove, graphene film prepared by the oxide-reduction method adding 0.1% in Sn-Ag-Cu solder can significantly improve wettability and the mechanical property of solder.As can be seen here, Graphene has broad application prospects in strengthening solder, raising solder performance etc.
At present, the preparation method that Graphene is conventional has three kinds of methods such as mechanical stripping method, redox graphite method, chemical vapour deposition technique.The Graphene quality that mechanical stripping method is prepared is high, but complex process, and productive rate is low, is difficult to practical application.Although redox graphite method has the features such as cost is low, output is large, technique is more complicated, and graphene-structured is destroyed seriously, blemish is extremely many, the poor-performing such as electricity and mechanics.Graphene size prepared by chemical vapour deposition technique is large, defect is few, but preparation temperature is higher and the time is long, efficiency is low, is difficult to practical application.
Because the preparation technology of grapheme material limits, result in Graphene strengthens in the preparation method of composite soldering, there are two difficult points: (1) graphene dispersion sex chromosome mosaicism, the mechanical ball milling of tradition is difficult to realize dispersed in composite soldering of Graphene, realize the dispersed of Graphene usually through chemical modification method, technique is more complicated.(2) graphene-structured defect problem, requires and addition demand according to actual preparation technology, and the normal Graphene adopting redox graphite method to obtain, in composite soldering, graphene-structured defect is more for this reason.Due at relatively high temperatures, the Graphene of structural failure very easily reacts to each other with active element in composite soldering, limits the extensive use of grapheme material in composite soldering.
Summary of the invention
The present invention will solve conventional method and prepare when Graphene strengthens copper base composite soldering that the graphene dispersion that exists is poor, blemish is many, preparation temperature is high and inefficient problem, and provides a kind of efficient cryogenic to prepare the method for Graphene enhancing copper base composite soldering.
Efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering, specifically carries out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 18sccm ~ 22sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 190Pa ~ 210Pa, and under pressure is 190Pa ~ 210Pa and hydrogen atmosphere in 40min by temperature most 500 DEG C ~ 700 DEG C, and be incubated 25min ~ 35min at temperature is 500 DEG C ~ 700 DEG C;
Two, pass into argon gas and carbon-source gas, the gas flow regulating hydrogen is 40sccm, argon gas flow is 80sccm, the gas flow of carbon-source gas is 1sccm ~ 8sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 800Pa ~ 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 190W ~ 210W, pressure is 800Pa ~ 1000Pa and temperature is deposit under 500 DEG C ~ 700 DEG C conditions, sedimentation time is 10s ~ 300s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue with the gas flow of hydrogen as 40sccm, argon gas flow is that 80sccm passes into hydrogen and argon gas, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 150Pa ~ 200Pa, under pressure is 150Pa ~ 200Pa and hydrogen and argon gas atmosphere, is 500 DEG C ~ 700 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal dust or alloy powder and step 2 is put into ball mill, carry out grinding and be stirred to powder and mix, namely obtain Graphene and strengthen copper base composite soldering.
The invention has the beneficial effects as follows: 1, the present invention utilizes plasma reinforced chemical vapour deposition method (PECVD), can by carbon source (CH by action of radio
4) resolve into very fast there is mutually highly active carbon-based group, through metallic catalyst catalytic reaction just can the short time grow Graphene in metal surface.Low temperature can be realized and effectively go out Graphene in the superficial growth of Cu powder.
2, the present invention utilizes plasma to strengthen action of radio, not only avoid high temperature pyrolysis carbon-source gas, and increases substantially carbon-source gas (CH
4) decomposition efficiency, namely pass into a small amount of carbon-source gas (CH
4) also can produce a large amount of activated carbon groups, thus effectively reduce preparation temperature, improve preparation efficiency.
3, method of the present invention is simple, and efficiently, low cost, is convenient to suitability for industrialized production, and the quality that the Graphene prepared strengthens Graphene in copper base composite soldering is high and dispersed, effectively can improve the performance of copper base composite soldering.
The present invention is used for a kind of efficient cryogenic and prepares the method that Graphene strengthens copper base composite soldering.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of Graphene/copper composite powder in embodiment one; 1 is D peak; 2 is G peak; 3 is 2D peak;
Fig. 2 is that in embodiment one, Graphene transfers to SiO
2the light microscope figure of/Si substrate;
Fig. 3 is that in embodiment one, Graphene transfers to SiO
2the Raman spectrogram of/Si substrate; 1 is D peak; 2 is G peak; 3 is 2D peak.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: a kind of efficient cryogenic described in present embodiment prepares the method that Graphene strengthens copper base composite soldering, specifically carries out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 18sccm ~ 22sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 190Pa ~ 210Pa, and under pressure is 190Pa ~ 210Pa and hydrogen atmosphere in 40min by temperature most 500 DEG C ~ 700 DEG C, and be incubated 25min ~ 35min at temperature is 500 DEG C ~ 700 DEG C;
Two, pass into argon gas and carbon-source gas, the gas flow regulating hydrogen is 40sccm, argon gas flow is 80sccm, the gas flow of carbon-source gas is 1sccm ~ 8sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 800Pa ~ 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 190W ~ 210W, pressure is 800Pa ~ 1000Pa and temperature is deposit under 500 DEG C ~ 700 DEG C conditions, sedimentation time is 10s ~ 300s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue with the gas flow of hydrogen as 40sccm, argon gas flow is that 80sccm passes into hydrogen and argon gas, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 150Pa ~ 200Pa, under pressure is 150Pa ~ 200Pa and hydrogen and argon gas atmosphere, is 500 DEG C ~ 700 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal dust or alloy powder and step 2 is put into ball mill, carry out grinding and be stirred to powder and mix, namely obtain Graphene and strengthen copper base composite soldering.
Involved efficient cryogenic in present embodiment prepares the general principle that Graphene strengthens copper base composite soldering: utilize plasma reinforced chemical vapour deposition method (PECVD), can by carbon source (CH by action of radio
4) resolve into carbon-based group very fast, these carbon-based groups have very high activity, through metallic catalyst catalytic reaction just can the short time grow Graphene in metal surface.In addition due to action of radio, not only avoid high temperature pyrolysis carbon-source gas, and increase substantially carbon-source gas (CH
4) decomposition efficiency, namely pass into a small amount of carbon-source gas (CH
4) also can produce a large amount of activated carbon groups, thus effectively reduce preparation temperature, improve preparation efficiency.Selected by the present invention, copper is as matrix, because the solubility of carbon atom in copper is relatively low, therefore can by the mode growing graphene of carbon atom absorption from restriction, not only quality is high for the Graphene that this kind of mode is formed, and good dispersion.The Graphene that should prepare in this way strengthens copper powders to make copper base composite soldering, and composite soldering can be made to obtain a series of outstanding character.
The beneficial effect of present embodiment is: 1, present embodiment utilizes plasma reinforced chemical vapour deposition method (PECVD), can by carbon source (CH by action of radio
4) resolve into very fast there is mutually highly active carbon-based group, through metallic catalyst catalytic reaction just can the short time grow Graphene in metal surface.Low temperature can be realized and effectively go out Graphene in the superficial growth of Cu powder.
2, present embodiment utilizes plasma to strengthen action of radio, not only avoid high temperature pyrolysis carbon-source gas, and increases substantially carbon-source gas (CH
4) decomposition efficiency, namely pass into a small amount of carbon-source gas (CH
4) also can produce a large amount of activated carbon groups, thus effectively reduce preparation temperature, improve preparation efficiency.
3, the method for present embodiment is simple, and efficiently, low cost, is convenient to suitability for industrialized production, and the quality that the Graphene prepared strengthens Graphene in copper base composite soldering is high and dispersed, effectively can improve the performance of copper base composite soldering.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: the copper powder purity described in step one is 99% ~ 99.99%, and particle diameter is 100nm ~ 100 μm.Other is identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two unlike: the carbon-source gas described in step 2 is methane.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: the metal dust purity described in step 3 is 99% ~ 99.99%, and particle diameter is 100nm ~ 100 μm; Described alloy powder purity is 99% ~ 99.99%, and particle diameter is 100nm ~ 100 μm.Other is identical with detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: the metal dust described in step 3 is Sn powder, Ag powder, P powder or Mn powder.Other is identical with detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: the alloy powder described in step 3 is Sn-Ag powder or Ag-Zn powder.Other is identical with detailed description of the invention one to five.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
A kind of efficient cryogenic described in the present embodiment prepares the method that Graphene strengthens copper base composite soldering, specifically carries out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 20sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, and under pressure is 200Pa and hydrogen atmosphere in 40min by temperature most 600 DEG C, and be incubated 30min at temperature is 600 DEG C;
Two, argon gas and CH is passed into
4, adjustment hydrogen gas flow is 40sccm, argon gas flow is 80sccm and CH
4gas flow is 2sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 1000Pa and temperature is deposit under 600 DEG C of conditions, sedimentation time is 60s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, to continue with hydrogen gas flow as 40sccm and argon gas flow as 80sccm passes into argon gas and hydrogen, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, under pressure is 200Pa and hydrogen and argon gas atmosphere, is 600 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal Sn powder and step 2 is put into ball mill, carry out grinding and stir 45min and mix to powder, namely obtain Graphene and strengthen copper base composite soldering.
Copper powder purity described in step one is 99.9% ~ 99.95%, and particle diameter is 300 orders.
Metal Sn powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
As shown in Figure 1,1 is D peak to the Raman spectrogram of the Graphene/copper composite powder prepared in embodiment one; 2 is G peak; 3 is 2D peak; Optical maser wavelength is 488nm; Illustrate that the quality of materials of acquisition is good as seen from the figure;
Graphene can only be transferred to SiO by the optical microscope inspection for Graphene
2on/Si matrix, Graphene transfers to SiO
2the light microscope figure of/Si substrate is as described in 2, and Graphene transfers to SiO
2as described in Figure 3,1 is D peak to the Raman spectrogram of/Si substrate; 2 is G peak; 3 is 2D peak; Do not have obvious mass defect after known transfer, size uniformity, also do not have before transfer, convenient transfer is also one of advantage of PECVD method.
The quality that the Graphene prepared strengthens Graphene in copper base composite soldering is high and dispersed, effectively can improve the performance of copper base composite soldering.
Embodiment two:
A kind of efficient cryogenic described in the present embodiment prepares the method that Graphene strengthens copper base composite soldering, specifically carries out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 20sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, and under pressure is 200Pa and hydrogen atmosphere in 40min by temperature most 500 DEG C, and be incubated 30min at temperature is 500 DEG C;
Two, argon gas and CH is passed into
4, adjustment hydrogen gas flow is 40sccm, argon gas flow is 80sccm and CH
4gas flow is 2sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 1000Pa and temperature is deposit under 500 DEG C of conditions, sedimentation time is 90s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, to continue with hydrogen gas flow as 40sccm and argon gas flow as 80sccm passes into argon gas and hydrogen, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, under pressure is 200Pa and hydrogen and argon gas atmosphere, is 500 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal Sn powder and step 2 is put into ball mill, carry out grinding and stir 45min and mix to powder, namely obtain Graphene and strengthen copper base composite soldering.
Copper powder purity described in step one is 99.9% ~ 99.95%, and particle diameter is 300 orders.
Metal Sn powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size uniformity in Graphene/copper composite powder that the present embodiment is prepared, defect is little, and Graphene major part is 1-3 layer.
The quality that the Graphene prepared strengthens Graphene in copper base composite soldering is high and dispersed, effectively can improve the performance of copper base composite soldering.
Embodiment three:
A kind of efficient cryogenic described in the present embodiment prepares the method that Graphene strengthens copper base composite soldering, specifically carries out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 20sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, and under pressure is 200Pa and hydrogen atmosphere in 40min by temperature most 600 DEG C, and be incubated 30min at temperature is 600 DEG C;
Two, argon gas and CH is passed into
4, adjustment hydrogen gas flow is 40sccm, argon gas flow is 80sccm and CH
4gas flow is 8sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 1000Pa and temperature is deposit under 600 DEG C of conditions, sedimentation time is 10s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, to continue with hydrogen gas flow as 40sccm and argon gas flow as 80sccm passes into argon gas and hydrogen, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, under pressure is 200Pa and hydrogen and argon gas atmosphere, is 600 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal Sn powder and step 2 is put into ball mill, carry out grinding and stir 45min and mix to powder, namely obtain Graphene and strengthen copper base composite soldering.
Copper powder purity described in step one is 99.9% ~ 99.95%, and particle diameter is 300 orders.
Metal Sn powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size uniformity in Graphene/copper composite powder that the present embodiment is prepared, defect is little, and Graphene major part is 1-3 layer.
The quality that the Graphene prepared strengthens Graphene in copper base composite soldering is high and dispersed, effectively can improve the performance of copper base composite soldering.
Embodiment four:
A kind of efficient cryogenic described in the present embodiment prepares the method that Graphene strengthens copper base composite soldering, specifically carries out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 20sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, and under pressure is 200Pa and hydrogen atmosphere in 40min by temperature most 600 DEG C, and be incubated 30min at temperature is 600 DEG C;
Two, argon gas and CH is passed into
4, adjustment hydrogen gas flow is 40sccm, argon gas flow is 80sccm and CH
4gas flow is 8sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 1000Pa and temperature is deposit under 600 DEG C of conditions, sedimentation time is 30s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, to continue with hydrogen gas flow as 40sccm and argon gas flow as 80sccm passes into argon gas and hydrogen, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, under pressure is 200Pa and hydrogen and argon gas atmosphere, is 600 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal A g powder and step 2 is put into ball mill, carry out grinding and stir 45min and mix to powder, namely obtain Graphene and strengthen copper base composite soldering.
Copper powder purity described in step one is 99.9% ~ 99.95%, and particle diameter is 300 orders.
Metal A g powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size uniformity in the Graphene/copper composite powder prepared in the present embodiment, defect is less, and Graphene major part is 3-5 layer.
The quality that the Graphene prepared strengthens Graphene in copper base composite soldering is high and dispersed, effectively can improve the performance of copper base composite soldering.
Embodiment five:
A kind of efficient cryogenic described in the present embodiment prepares the method that Graphene strengthens copper base composite soldering, specifically carries out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 20sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, and under pressure is 200Pa and hydrogen atmosphere in 40min by temperature most 700 DEG C, and be incubated 30min at temperature is 700 DEG C;
Two, argon gas and CH is passed into
4, adjustment hydrogen gas flow is 40sccm, argon gas flow is 80sccm and CH
4gas flow is 8sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 1000Pa and temperature is deposit under 700 DEG C of conditions, sedimentation time is 30s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, to continue with hydrogen gas flow as 40sccm and argon gas flow as 80sccm passes into argon gas and hydrogen, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 200Pa, under pressure is 200Pa and hydrogen and argon gas atmosphere, is 700 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal A g powder and step 2 is put into ball mill, carry out grinding and stir 45min and mix to powder, namely obtain Graphene and strengthen copper base composite soldering.
Copper powder purity described in step one is 99.9% ~ 99.95%, and particle diameter is 300 orders.
Metal A g powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size uniformity in Graphene/copper composite powder that the present embodiment is prepared, defect is few, and Graphene major part is more than 3 layers.
The quality that the Graphene prepared strengthens Graphene in copper base composite soldering is high and dispersed, effectively can improve the performance of copper base composite soldering.
Claims (6)
1. efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering, it is characterized in that carrying out according to following steps:
One, copper powder is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, be that 18sccm ~ 22sccm passes into hydrogen with gas flow, vacuum pumping rate is regulated to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 190Pa ~ 210Pa, and under pressure is 190Pa ~ 210Pa and hydrogen atmosphere in 40min by temperature most 500 DEG C ~ 700 DEG C, and be incubated 25min ~ 35min at temperature is 500 DEG C ~ 700 DEG C;
Two, pass into argon gas and carbon-source gas, the gas flow regulating hydrogen is 40sccm, argon gas flow is 80sccm, the gas flow of carbon-source gas is 1sccm ~ 8sccm, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 800Pa ~ 1000Pa, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 190W ~ 210W, pressure is 800Pa ~ 1000Pa and temperature is deposit under 500 DEG C ~ 700 DEG C conditions, sedimentation time is 10s ~ 300s, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue with the gas flow of hydrogen as 40sccm, argon gas flow is that 80sccm passes into hydrogen and argon gas, and regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum plant as 150Pa ~ 200Pa, under pressure is 150Pa ~ 200Pa and hydrogen and argon gas atmosphere, is 500 DEG C ~ 700 DEG C from temperature is cooled to room temperature, namely Graphene/copper composite powder is obtained,
Three, Graphene/copper composite powder prepared by metal dust or alloy powder and step 2 is put into ball mill, carry out grinding and be stirred to powder and mix, namely obtain Graphene and strengthen copper base composite soldering.
2. a kind of efficient cryogenic according to claim 1 prepares the method that Graphene strengthens copper base composite soldering, and it is characterized in that the copper powder purity described in step one is 99% ~ 99.99%, particle diameter is 100nm ~ 100 μm.
3. a kind of efficient cryogenic according to claim 1 prepares the method that Graphene strengthens copper base composite soldering, it is characterized in that the carbon-source gas described in step 2 is methane.
4. a kind of efficient cryogenic according to claim 1 prepares the method that Graphene strengthens copper base composite soldering, and it is characterized in that the metal dust purity described in step 3 is 99% ~ 99.99%, particle diameter is 100nm ~ 100 μm; Described alloy powder purity is 99% ~ 99.99%, and particle diameter is 100nm ~ 100 μm.
5. a kind of efficient cryogenic according to claim 1 prepares the method that Graphene strengthens copper base composite soldering, it is characterized in that the metal dust described in step 3 is Sn powder, Ag powder or Mn powder.
6. a kind of efficient cryogenic according to claim 1 prepares the method that Graphene strengthens copper base composite soldering, it is characterized in that the alloy powder described in step 3 is Sn-Ag powder or Ag-Zn powder.
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